MIL-53(Fe) Metal–Organic Frameworks (MOFs) as an Efficient and Reusable Catalyst for the One-Pot Four-Component Synthesis of Pyrano[2,3-c]-pyrazoles

Article abstract of DOI:10.1002/aoc.4679

A novel and simple approach for the efficient and rapid synthesis of pyrano[2,3-c]-pyrazoleshas been accomplished via the four-component condensation reaction of malononitrile, hydrazine hydrate, ethyl acetoacetate, and substituted aldehydes using MIL-53(

Full text of DOI:10.1002/aoc.4679

Received: 16 August 2018
DOI: 10.1002/aoc.4679
Revised: 1 October 2018
Accepted: 10 October 2018
F U L L P A P E R
MIL‐53(Fe) Metal–Organic Frameworks (MOFs) as an
Efficient and Reusable Catalyst for the One‐Pot Four‐
Component Synthesis of Pyrano[2,3‐c]‐pyrazoles
Mohammad Ali Ghasemzadeh
| Boshra Mirhosseini‐Eshkevari |
Mohammad Hossein Abdollahi‐Basir
Department of Chemistry, Qom Branch,
A novel and simple approach for the efficient and rapid synthesis of
Islamic Azad University, Post Box: 37491‐
3191, Qom, I. R. Iran
1
pyrano[2,3‐c]‐pyrazoleshas been accomplished via the four‐component conden-
sation reaction of malononitrile, hydrazine hydrate, ethyl acetoacetate, and
substituted aldehydes using MIL‐53(Fe) metal–organic framework (MOF) as a
catalyst in ethanol at room temperature. Recycling studies have shown that
the MIL‐53(Fe) can be readily recovered and reused six times without significant
loss of its activity. The present protocol offers the advantages including short
reaction times, simple workup, high yields, elimination of toxic solvents, no
chromatographic purification and recoverability of the catalyst. Also, the cata-
lyst was fully characterized by SEM, EDX, FT‐IR, XRD, TGA and TEM analysis.
Correspondence
Mohammad Ali Ghasemzadeh,
Department of Chemistry, Qom Branch,
Islamic Azad University, Post Box: 37491–
13191, Qom, I. R. Iran.
Email: ghasemzadeh@qom‐iau.ac.ir
Funding information
Islamic Azad University, Qom Branch,
Qom, I. R. Iran, Grant/Award Number:
grant number 2014‐13929
KEYWORDS
metal–organic framework, MIL‐53(Fe), multi‐component reactions, pyrano[2,3‐c]‐pyrazoles
[
5]
1
| INTRODUCTION
range of biological activities including anticancer anti‐
[
6]
[7]
inflammatory,
activities.
antimicrobial,
and molluscicidal
[
8,9]
Multicomponent reactions (MCRs) cause the formation of
numerous bonds in a sole action and are attracting grow-
ing consideration as one of the strongest appearing syn-
thetic gadget for the creation of molecular variety and
complexity. In addition, the finding of new MCRs can
be considered as an engrossing subject for academic
research, which also satisfies an applied interest of practi-
cal science. The main advantages of MCRs consist of
shorter reaction times, economical, energy saving, lower
costs, and the avoidance of time consuming and expen-
sive purification processes. It is determinate that MCRs
Methods reported in the literature for synthesis of
pyranopyrazoles in the presence of various catalysts are
[
10]
[11]
[12]
including per‐6‐ABCD,
[Dsim] AlCl ,
[DBU][Ac],
4
[1]
[13]
[14]
[15]
TEABr,
amberlyst A21,
L‐Proline,
[CHCl]
[
16]
[17]
[ZnCl ] , FeNi /SiO /HPGMNP, [(CH ) SO ‐HMIM]
[HSO4], silicotungstic acid and NaOH/microwave.
2
2
3
2
2 4
3
[
18]
[19]
[20]
[2]
Many of these reports suffer from different restrictions
and weaknesses, such as use of long reaction time, expen-
sive reagents and catalysts, hard reaction conditions, low
product yield, nonrecyclable, dangerous organic solvents,
limiting their scope for use in practical applications.
Therefore, development of green protocols for heterocy-
clic synthesis involving easy and environmentally
friendly procedures would be effective and desirable.
Metal–organic frameworks (MOFs) are crystalline
solids makes by inorganic clusters or metal ions linked
by bi‐or multifunctional organic ligands. Exploiting the
[
3]
are commonly much more environmentally benign.
Due to their considerable and diverse biological activi-
ties, design and expansion of new methods for the construc-
tion of applied spirooxindoles have drawn significant favorite
[4]
from the synthetic, organic as well as medicinal chemists.
From the literature we comprehend that
dihydropyrano[2,3‐c] pyrazole scaffolds display a vast
Appl Organometal Chem. 2018;e4679.
wileyonlinelibrary.com/journal/aoc
© 2018 John Wiley & Sons, Ltd.
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https://doi.org/10.1002/aoc.4679

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GHASEMZADEH ET AL.
benefits of the MOFs such as flexibility in designing the
active sites, high metal content, tunable pore size, large
surface area, would be an ingenious idea to make new
[21,22]
catalysts.
Recently, MOFs have been shown to have applica-
[
23]
[24]
SCHEME 1 Synthesis of pyrano[2,3‐c]‐pyrazoles using MIL‐
tions such as for magnetism,
catalysis,
nonlinear
separations of gases,
as well as for heterogeneous
[25]
[26]
53(Fe) in ethanol at room temperature
optical activity, adsorption,
[27,28]
storage and purification
[29]
[30]
[31]
catalysis,
sensing
and drug release/delivery
and
commercial reagent grade and were used without fur-
ther purification. All melting points are uncorrected
and were determined in capillary tube on Boetius melt-
[
32]
many other fields.
According to their unique inorganic–organic hybrid
nature and nanometer porous structures, MOFs are rich
in basic feature which promise revolutionary new appara-
tus concepts. Most of the studies in the past focused on
the rational design, synthesis, properties, and applications
of MOFs in their micro‐sized cubic crystals obtained from
traditional MOF synthesis reaction.
In our continuation to develop efficient, environmen-
tally friendly, green approaches inexpensive, economical
for synthesis of different heterocyclic compounds.
We recently reported various synthetic methods for
1
13
ing point microscope. H NMR and C NMR spectra
were obtained on Bruker 400 MHz spectrometer with
CDCl as solvent using TMS as an internal standard.
3
FT‐IR spectrum was recorded on Magna‐IR, spectrome-
ter 550. The elemental analyses (C, H, N) were obtained
from a Carlo ERBA Model EA 1108 analyzer. Powder X‐
ray diffraction (XRD) was carried out on a Philips dif-
fractometer of X'pert Company with mono chromatized
Cu Kα radiation (λ = 1.5406 Å). Microscopic morphol-
ogy of products was visualized by SEM (LEO 1455VP).
Transmission electron microscopy (TEM) was performed
with a Jeol JEM‐2100UHR, operated at 200 kV. The
mass spectra were recorded on a Joel D‐30 instrument
at an ionization potential of 70 eV. Magnetic properties
were obtained on a BHV‐55 vibrating sample magne-
tometer (VSM). The compositional analysis was done
by energy dispersive analysis of X‐ray (EDX, Kevex,
Delta ClassI). Thermogravimetric analysis (TGA) was
performed on a Mettler Toledo TGA under argonand
heated from room temperature to 825 °C. The approxi-
mate sample weight was 10 mg in TG experiment with
several
nanocatalysts.
biologically
interesting
products
using
[
33–37]
Hence, herein, a new approach using MIL‐53(Fe)
Figure 1) as highly efficient reusable catalyst is reported
for the synthesis of a series of some pyranopyrazole deriv-
atives by reaction of aromatic aldehydes, malononitrile,
hydrazine hydrate, and ethyl acetoacetate in ethanol as
solvent at room temperature (Scheme 1).
(
2
2
| EXPERIMENTAL
10 °C/min heating rate.
.1 | Materials and Instrumentation
Chemicals were purchased from the Sigma‐Aldrich and
Merck in high purity. All of the materials were of
2.2 | Preparation of MIL‐53(Fe)
The preparation procedure for the synthesis of
MIL‐53(Fe) is shown in scheme 2. MIL‐53(Fe) was
synthesized by a solvothermal method according to the
[
38]
previous report.
In a typical experiment, a mixture
of FeCl3, terephthalic acid (BDC) and N,N‐
dimethylformamide (DMF) with a molar ratio of
1:1:280 was mixed and sonicated for a few minutes, then
the reaction mixture was placed in a Teflon lined steel
autoclave, heating at 150 °C for 15 hr. When the reaction
was completed the light brown powder was obtained by
centrifuging and washed with DMF. Next the MIL‐
53(Fe) was kept under stirring in methanol for three
days. Finally, the solid powder was heated at 150 °C
FIGURE 1 The chemical structure of MIL‐53(Fe) Metal–organic
overnight to remove guest molecules (H O, DMF, and
2
Framework
methanol).

GHASEMZADEH ET AL.
3 of 8
SCHEME 2 Preparation of MIL‐53(Fe)
MOF
2
.3 | General procedure for the synthesis
6‐Amino‐4‐(2‐hydroxy‐5‐nitrophenyl)‐3‐methyl‐
of pyrano[2,3‐c]‐pyrazoles derivatives
2,4‐dihydropyrano[2,3‐c]pyrazole‐5‐carbonitrile (5p):
1
White powder, mp: 210–212 °C. H NMR (400 MHz,
A mixture of equimolar ratios of aldehydes (1 mmol),
malononitrile (1 mmol), hydrazine hydrate (1 mmol),
and ethyl acetoacetate (1 mmol) in the presence of MIL‐
DMSO‐d ) δ: 1.87 (s, 3H, CH ), 4.79 (s, 1H, CH), 7.03 (s,
6
3
2H, NH ), 7.21–7.25 (d, 1H, ArH), 7.90–8.02 (d, 1H,
2
ArH), 8.07–8.10 (d, 1H, ArH), 10.90 (s, 1H, OH), 12.02 (s,
13
5
3(Fe) MOF (0.005 g) as a catalyst was stirred in etha-
1H, NH); C NMR (100 MHz, DMSO‐d ) δ: 10.30, 29.18,
6
nol(10 ml) at room temperaturefor about 15 min. After
completion of the reaction as determined by thin layer
chromatography (TLC), the reaction mixture was dis-
solved in dichloromethane. The catalyst was insoluble
in CH Cl and was separated by simple filtration. The sol-
38.94, 40.96, 55.53, 104.85, 116.39, 121.16, 132.04, 135.83,
137.32, 144.02 159.73, 161.66. FT‐IR (KBr): 3425, 3302,
−
1
2580, 2198, 1666, 1400, 1254 cm ; Anal. Calcd. For
C H N O : C 53.68, H 3.54, N 22.36, O 20.43. Found C
1
4
11 5 4
+
53.64, H 3.48,N 22.32 O 20.38; MS (EI) (m/z): 313.08 (M ).
2
2
vent was evaporated and the residue was recrystallized
from ethanol to afford the pure product.
All the products were characterized and identified with
m.p., H NMR, C NMR and FT‐IR spectroscopy tech-
3 | RESULTS AND DISCUSSION
1
13
niques. Spectral data of the new products are given below.
In the preliminary experiments MIL‐53(Fe) MOF was
prepared and characterized by SEM, EDX, FT‐IR,XRD,
TGA and TEM analysis.
2
.4 | Spectral data of the new compounds
Scanning electron microscopy (SEM) is a useful tool
for determining the size distribution, particles shape,
and porosity. The morphology and particle size of MIL‐
6‐Amino‐4‐(4‐cyanophenyl)‐3‐methyl‐2,4‐
dihydropyrano[2,3‐c]pyrazole‐5‐carbonitrile. (5n): White
1
powder, mp: 211–213 °C. H NMR (400 MHz, DMSO‐d )
6
δ: 1.82 (s, 3H, CH ), 4.78 (s, 1H, CH), 7.06 (s, 2H, NH ),
3
2
7
1
3
1
2
.40–7.43 (d, 2H, ArH), 7.82–7.85 (d,2H, ArH) 12.22 (s,
13
H, NH); C NMR (100 MHz, DMSO‐d ) δ: 10.18, 36.62,
6
9.01, 41.01, 56.54, 97.13, 110.12, 119.27, 120.95, 129.08,
33.08, 136.129, 150.53, 161.61. FT‐IR (KBr): 3483,3234,
−
1
229, 1643, 1410, 1493, 1057 cm ; Anal. Calcd. For
C H N O: C 64.97, H 4.00, N 25.26, O 5.77. Found C
1
5
11 5
+
6
4.89, H 4.23; N 25.22, O 5.69; MS (EI) (m/z): 277.10 (M ).
‐Amino‐4‐(5‐bromo‐2‐hydroxyphenyl)‐3‐methyl‐
,4‐dihydropyrano[2,3‐c]pyrazole‐5‐carbonitrile (5o):
White powder, mp: 212–214 °C. H NMR (400 MHz,
DMSO‐d ) δ: 2.05 (s, 3H, CH ), 4.66 (s, 1H, CH), 6.82 (s,
6
2
1
6
3
2
H, NH ), 6.95–6.98 (d, 1H, ArH), 7.16 (d, 1H,
2
ArH),7.36–7.40(d,1H,ArH), 10.42 (s, 1H, OH), 12.50 (s,
1
3
1
2
1
3
H, NH); C NMR (100 MHz, DMSO‐d ) δ: 10.32,
6
9.11, 38.95, 40.97, 55.29, 105.04, 116.10, 118.04, 121.03,
26.06, 131.65, 137.18, 148.29, 160.29. FT IR (KBr): 3458,
352, 2924, 2187,1608,1477,1227 cm ; Anal. Calcd. For
−
1
C H BrN O : C 48.44, H 3.19, Br 23.02, N 16.14, O
14
11
4 2
9
.22. Found C 48.32, H 3.14; Br 23.00, N 16.10, O 9.18;
+
MS (EI) (m/z): 346.01 (M ).
FIGURE 2 SEM image of MIL‐53(Fe) MOF

4
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GHASEMZADEH ET AL.
5
3(Fe) MOF was determined by (SEM), MIL‐53(Fe) MOF
Figure 3 shows that the elemental compositions are the
(C, O, N and Fe) of MIL‐53(Fe) MOF.
displayed a rod shape (Figure 2).
The chemical purity of the samples as well as their
stoichiometry was tested by using EDX analysis.
The FT‐IR spectrum of MIL‐53(Fe) is shown in
Figure 4. The spectrum of this MOF exhibited band (Ar
FIGURE 3 EDX spectrum of MIL‐
53(Fe) MOF
FIGURE 4 FT‐IR spectrum of MIL‐53(Fe) MOF
FIGURE 5 XRD diffraction pattern of
MIL‐53(Fe) MOF

GHASEMZADEH ET AL.
5 of 8
FIGURE 6 TGA curve of MIL‐53(Fe)
MOF under Ar atmosphere
−
1 [38]
C‐H) assigning to aromatic group at 731 cm ,
and
The powder X‐ray diffraction (PXRD) pattern of MIL‐
53(Fe) (Figure 5) shows that the as‐obtained sample was
crystalline, and the diffraction peaks were coincident
with the previously reported MOF MIL‐53 as well as the
simulated one, confirming the successful synthesis of
MIL‐53(Fe). The characteristic peaks were at 2θ of 9.3°,
−
1
C=O stretching vibration at 1685 cm .The two sharp
peaks at 1396 cm and 1540 cm were corresponded
to the symmetrical vibration and asymmetrical vibration
−
1
−1
−
of COO , respectively, reflecting of the presence of the
[39]
dicarboxylate linker.
The Fe‐O band between the
carboxylic group of terephthalic acid and Fe (III) at
−
1
5
59 cm was clearly observed in MIL‐53(Fe).
FIGURE 8 The effect of various catalysts on the model reaction
FIGURE 7 TEM image of MIL‐53(Fe) MOF
SCHEME 3 The model reaction for the synthesis of pyrano[2,3‐
c]‐pyrazole
FIGURE 9 The effect of catalyst amount on the model reaction

6
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GHASEMZADEH ET AL.
1
2.7°, 17.6°, 18.5°, 25.5° and 27.3°, thus demonstrated
frameworks. When the temperature attained 500–800 °C,
little change in the TG curve was observed.
that pure MIL‐53(Fe) was prepared successfully in this
condition.
[38]
The morphology and particle size of the MIL‐53(Fe)
sample were examined by transmission electron micros-
copy (TEM). The TEM image of MIL‐53(Fe) is illustrated in
Figure 7. The TEM image reveals that small rod particles of
50–200 nm which confirms with the result of SEM image.
Initially, to obtain the best reaction conditions, we
selected reaction of malononitrile, hydrazine hydrate,
ethyl acetoacetate, and 4‐nitrobenzaldehyde as model
reaction. Different catalysts and solvents were examined
in the four‐component preparation of pyrano[2,3‐c]‐
pyrazole (Scheme 3).
Figure 6 shows the Thermogravimetric analysis (TGA)
curve of MIL‐53(Fe). The MIL‐53(Fe) exhibited two‐stage
weight loss in the TGA curve. MIL‐53 (Fe) showed the ini-
tial weight loss below 340 °C (30%–40%), which was attrib-
uted to the loss of solvents from the framework. The
second weight loss (in the range from 340 to 500 °C
(40%–50%) showed the collapse of MIL‐53(Fe) structure
due to the removal of structural organic ligands from their
Initially, the model study was carried out using 0.01 g
of several catalysts including MgO, CuI, Co O , Cu (BDC)
3
4
and MIL‐53(Fe). As shown in Figure 8, it was observed
that MIL‐53(Fe) exhibited high activity in comparison
with other catalysts and the corresponding product was
performed in excellent yield and short reaction time.
Next, different amounts of the MIL‐53(Fe) were
applied in the model reaction. It was observed that no
product was obtained in the absence of the catalyst. As
shown in Figure 9, 0.005 g of the MIL‐53(Fe) was the best
operative experimental conditions. With increase the
amount of the catalyst we did not observe any consider-
able change in the reaction time and product yield,
whereas decreasing the amount of catalyst leads to
decrease in the product yield. Hence, the best amount of
FIGURE 10 The effect of different solvents on the model
reaction
TABLE 1 Synthesis of pyrano[2,3‐c] pyrazoles using MIL‐53(Fe) MOF
a
o
o
Entry
Ar
product
Time (min)
Yield (%)
M.p. C
Lit. M.p. C
[
[
[
[
[
[
[
[
[
[
[
[
[
20]
20]
20]
20]
20]
20]
20]
20]
40]
40]
40]
40]
40]
1
2
3
4
5
6
7
8
9
H
5a
5b
5c
20
14
15
16
12
20
10
18
17
13
17
16
12
20
17
19
91
88
98
88
92
90
90
95
85
91
92
86
93
85
87
89
204–206
212–214
207–209
202–204
208–210
198–200
199–201
212–214
143–145
256–258
240–241
213–215
208–210
211–213
212–214
210–212
206–208
214–216
209–211
204–206
210–212
200–202
201–203
214–216
145–147
258–260
241–243
215–216
210–212
4‐Cl
4‐ NO
4‐Br
4‐F
2
5d
5e
4‐ OCH
4‐CH
3
5f
3
5 g
5 h
5i
4‐S CH
3
2‐Cl
1
1
1
1
1
1
1
0
1
2
3
4
5
6
2‐F
5j
4‐Et
5 k
5 l
5 m
5n
5o
5p
2,3‐(OMe)
2
4‐OH
b
4‐CN
‐‐‐‐‐‐
b
5‐Br,2‐OH
‐‐‐‐‐‐
b
2‐OH,5‐NO
2
‐‐‐‐‐‐
a
Isolated yield.
b
New Products.

GHASEMZADEH ET AL.
7 of 8
MIL‐53(Fe) was selected 0.005 g in the model reaction
(Figure 9).
Then, the effect of solvent was investigated when the
model was carried out in the presence of MIL‐53(Fe) using
different solvents such as EtOH, CH CN, DMF, and PhCH3
3
and also under solvent‐free conditions at room tempera-
ture. The summarized results of Figure 10 show that the
best results were obtained using ethanol as solvent.
To assess the versatility of this procedure a series of
aromatic aldehydes were studied under the optimum
reaction conditions. The aldehydes having both the
electron‐donating and electron‐withdrawing substituents
on the aryl ring gave the products in good to excellent
yields in very short reaction times; the results are listed in
Table 1.
SCHEME
4
Proposed mechanism for the synthesis of
3.1 | Reuse of Catalyst
pyrano[2,3‐c]pyrazoles
The reusability of the catalyst was examined by repeating
the model reaction using MIL‐53(Fe) under optimized
reactions. It was found that the MIL‐53(Fe) catalyst could
be recovered and reused six times without a significant
degradation in catalytic activity (Figure 11).
tautomerization afford the desired pyranopyrazole
derivatives (5).
4 | CONCLUSIONS
A
plausible mechanism for the synthesis of
pyrano[2,3‐c] pyrazoles using MIL‐53(Fe) as catalyst is
depicted in scheme 4. On the basis of the experimental
results were examined together with those in the litera-
In summary, we have developed a green and highly effi-
cient approach for the one‐pot four‐component synthesis
of pyrano[2,3‐c] pyrazole derivatives using MIL‐53(Fe) at
room temperature. The advantages of this method are
short reaction time, clean reaction, high yield, easy purifi-
cation; non‐toxic and economic availability of the catalyst.
This catalyst can be recovered easily and reused over sev-
eral reaction cycles without substantial loss of reactivity.
[14]
ture.
It is likely that MIL‐53(Fe) acts as a Lewis acid,
increase the electrophilicity of the carbonyl group on
the aldehyde by means of a strong coordinate bond. In
the first step, 2‐arylidenemalononitrile (3) is formed by
a fast Knoevenagel condensation of malononitrile with
arylaldehyde catalyzed by the MIL‐53(Fe). The second
step involves formation of 3‐methyl‐1H‐pyrazol‐5(4H)‐
one (1) by the reaction of hydrazine hydrate with ethyl
acetoacetate. In the third step, a Michael addition of 2
to 3 in the presence of the catalyst produced the interme-
diate (4). Intramolecular cyclization and subsequently
ACKNOWLEDGMENTS
The author gratefully acknowledges the financial support
of this work by the Research Affairs Office of the Islamic
Azad University, Qom Branch, Qom, I. R. Iran [grant
number 2014‐13929].
ORCID
Mohammad Ali Ghasemzadeh
002-8309-6727
http://orcid.org/0000-
0
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FIGURE 11 Reusability of the MIL‐53(Fe) MOF

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